Process for isomerization and decarboxylation of unsaturated organic compounds with a metal catalyst or catalyst precursor

ABSTRACT

Disclosed is a method for using a metal catalyst or catalyst precursor that catalyzes the isomerization of an unsaturated fatty acid, unsaturated fatty acid derivative, or an unsaturated triglyceride. Also disclosed is a method for using a metal catalyst or catalyst precursor that catalyzes the decarboxylation of an unsaturated organic compound. Also disclosed is a method for using a catalyst or catalyst precursor for the dual function isomerization and decarboxylation of an unsaturated fatty acid to an unsaturated organic compound.

CROSS-REFERENCE TO RELATED APPLICATION

This present application claims priority under 35 U.S.C. §119(e) to U.S.Provisional Ser. No. 61/788,192, which was filed on Mar. 15, 2013, andis hereby incorporated by reference.

FIELD OF INVENTION

This invention relates to the use of a metal catalyst or catalystprecursor that catalyzes the isomerization of an unsaturated fatty acid,unsaturated fatty acid derivative, alkene, or an unsaturatedtriglyceride. Also disclosed is the use of a metal catalyst or catalystprecursor that catalyzes the decarboxylation of an unsaturated organiccompound. Also disclosed is the use of a catalyst or catalyst precursorfor the dual function isomerization and decarboxylation of anunsaturated fatty acid to an unsaturated organic compound.

BACKGROUND OF INVENTION

Research has focused on the process of converting bio-based fatty acidsand their derivatives to olefins or isomerized fatty compounds forvaluable industrial applications. Preferably, this process would utilizea low cost feedstock material such as unsaturated fatty acids,carboxylic acids, unsaturated fatty acid derivatives, alkenes, andconvert said reactants to a more commercially desirable product. Suchdesirable products include isomerized olefins, α-olefins, anddecarboxylated products.

In order to facilitate the isomerization of the alkene reactant, thereis a need to develop a low-cost catalyst and catalyst precursorcompounds to lower the activation energy of such a reaction and generatedesirable commercial end products. Preferably, the catalyst wouldfacilitate both the decarboxylation and isomerization of feedstockmaterial to generate the desirable end product. Alternatively, thecatalyst would either isomerize or decarboxylate feedstock material.Preferably the catalyst would be low cost material and have a highturnover number.

BRIEF SUMMARY OF THE INVENTION

Disclosed herein is a process for the production of an isomerizedunsaturated organic compound, the process comprising contacting anunsaturated fatty acid, unsaturated fatty acid derivative, or anunsaturated triglyceride in the presence of a catalyst or catalystprecursor containing ruthenium or osmium at a temperature at whichisomerization occurs and recovering the isomerized unsaturated organiccompound product, wherein the isomerization does not require the step ofadding a carboxylic acid anhydride and the catalyst or catalystprecursor does not contain a phosphine ligand.

In an embodiment of the invention, the process for the production of anisomerized unsaturated organic compound comprises an additional step ofcontacting an additional acid to an unsaturated fatty acid, unsaturatedfatty acid derivative, or an unsaturated triglyceride in the presence ofa catalyst or catalyst precursor. In another embodiment, the additionalacid is a monocarboxylic acid. In yet another embodiment of theinvention, the monocarboxylic acid is benzoic acid, cinnamic acid,propanoic acid, undecanoic acid, acetic acid, stearic acid, or oleicacid.

In an embodiment of the invention, the process for the production of anisomerized unsaturated organic compound utilizes a catalyst or catalystprecursor containing both ruthenium and osmium compounds. In anotherembodiment of the invention, the catalyst or catalyst precursor isselected from the group consisting of ruthenium carbonyl or rutheniumchloride. In yet another embodiment of the invention, the catalyst orcatalyst precursor is osmium carbonyl.

In another embodiment of the invention, the process for the productionof an isomerized unsaturated organic compound yields an olefin. In oneembodiment of the invention, the disclosed isomerization process yieldsan isomerized unsaturated organic compound product having a mixture ofinternal and α-olefins. In yet another embodiment of the invention, theisomerization process yields an isomerized unsaturated organic compoundproduct having a conjugated internal olefin.

In yet another embodiment of the invention, the process for theproduction of an isomerized unsaturated organic compound yields anolefin wherein the olefin is further subject to an oligomerization or apolymerization reaction. In one aspect of invention, the olefin productfrom the isomerization process is further subject to a metathesisreaction.

Disclosed herein a process for the production of a decarboxylatedunsaturated organic compound, the process comprising contacting acarboxylic acid in the presence of a catalyst or catalyst precursorcontaining ruthenium or osmium at a temperature at which decarboxylationoccurs and recovering the decarboxylated unsaturated organic compoundproduct, wherein the decarboxylation does not require the step of addinga carboxylic acid anhydride.

In an embodiment of the invention, the process for the production of adecarboxylated unsaturated carboxylic acid comprises the additional stepof contacting an additional acid to the carboxylic acid in the presenceof a catalyst or catalyst precursor. In another embodiment, theadditional acid is a monocarboxylic acid. In yet another embodiment ofthe invention, the monocarboxylic acid is benzoic acid, cinnamic acid,acetic acid, undecanoic acid, propanoic acid, stearic acid, or oleicacid.

In an embodiment of the invention, the process for the production of adecarboxylated unsaturated carboxylic acid utilizes a catalyst orcatalyst precursor containing both ruthenium and osmium compounds. Inanother embodiment of the invention, the catalyst or catalyst precursoris selected from the group consisting of ruthenium carbonyl or rutheniumchloride. In yet another embodiment of the invention, the catalyst orcatalyst precursor is osmium carbonyl.

In another embodiment of the invention, the process for the productionof a decarboxylated unsaturated carboxylic acid yields an olefin. In oneembodiment of the invention, the disclosed decarboxylation processyields a mixture of internal and α-olefins. In yet another embodiment ofthe invention, the decarboxylation process yields a decarboxylatedunsaturated carboxylic acid having a conjugated internal olefin.

In yet another embodiment of the invention, the process for theproduction of an decarboxylated unsaturated organic compound yields anolefin wherein the olefin is further subject to an oligomerization or apolymerization reaction. In one aspect of invention, the olefin productfrom decarboxylation process is further subject to a metathesisreaction.

Disclosed herein is a process for the isomerization and decarboxylationof an unsaturated organic compound, the process comprising contacting anunsaturated fatty acid in the presence of a catalyst or catalystprecursor containing ruthenium or osmium at a temperature at which theisomerization and decarboxylation occurs and recovering the isomerizedand decarboxylated unsaturated organic compound.

In an embodiment of the invention, the process of the production of anisomerized and decarboxylated unsaturated organic compound comprises anadditional step of contacting an additional acid to the unsaturatedfatty acid in the presence of a catalyst or catalyst precursor. Inanother embodiment, the additional acid is a monocarboxylic acid. In yetanother embodiment of the invention, the monocarboxylic acid is benzoicacid, cinnamic acid, propanoic acid, undecanoic acid, acetic acid,stearic acid, or oleic acid.

In an embodiment of the invention, the process for the production ofisomerized and decarboxylated unsaturated organic compound utilizes acatalyst or catalyst precursor containing both ruthenium and osmiumcompounds. In another embodiment of the invention, the catalyst orcatalyst precursor is selected from the group consisting of rutheniumcarbonyl or ruthenium chloride. In yet another embodiment of theinvention, the catalyst of catalyst precursor is osmium carbonyl.

In yet another embodiment of the invention, the process of theproduction of an isomerized and decarboxylated unsaturated organiccompound yields an olefin. In one embodiment of the invention, thedisclosed isomerization and decarboxylation process yields a mixture ofinternal and α-olefins. In yet another embodiment of the invention, theisomerization and decarboxylation process yields an unsaturated organiccompound product having a conjugated internal olefin.

Also disclosed is a process for the production of an isomerizedvegetable oil, the process comprising contacting a vegetable oil in thepresence of a catalyst or catalyst precursor containing ruthenium orosmium at a temperature at which isomerization occurs and recovering theisomerized vegetable oil product, wherein the isomerization does notrequire the step of adding a carboxylic acid anhydride and the catalystor catalyst precursor does not contain a phosphine ligand.

In an embodiment of the invention, the process for the production of anisomerized vegetable oil comprises an additional step of contactingvegetable oil in the presence of a catalyst or catalyst precursor. Inanother embodiment, the additional acid is a monocarboxylic acid. In yetanother embodiment of the invention, the monocarboxylic acid is benzoicacid, cinnamic acid, propanoic acid, undecanoic acid, acetic acid,stearic acid, or oleic acid.

In an embodiment of the invention, the process for the production of anisomerized vegetable oil utilizes a catalyst or catalyst precursorcontaining both ruthenium and osmium compounds. In another embodiment ofthe invention, the catalyst or catalyst precursor is selected from thegroup consisting of ruthenium carbonyl or ruthenium chloride. In yetanother embodiment of the invention, the catalyst or catalyst precursorcompound is osmium carbonyl.

In another embodiment of the invention, the process for the productionof an isomerized vegetable oil yields an olefin containing triglyceride.In one embodiment of the invention, the disclosed isomerized vegetableoil process yields an isomerized vegetable oil having a mixture ofinternal and α-olefins containing triglycerides. In yet anotherembodiment of the invention, the isomerization process yields anisomerized vegetable oil having a conjugated internal olefin.

In yet another embodiment of the invention, the process of theproduction of an isomerized vegetable oil utilizes soybean oil.

Also disclosed herein is a process for the isomerization and/ordecarboxylation of the unsaturated organic compound wherein the processdoes not require the step of adding a carboxylic anhydride.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention may best be understood from the following detaileddescriptions of the embodiments of the invention illustrated in thedrawings, wherein:

FIG. 1 is depiction of an exemplar reaction scheme for the isomerizationof an unsaturated organic compound to an isomerized α-olefin, wherein nis between 0-14 for the purposes of the figure.

FIG. 2 is a depiction of an exemplar reaction scheme for thedecarboxylation of an unsaturated carboxylic acid to produce anunsaturated organic compound.

FIG. 3 is a depiction of an exemplar reaction scheme for theisomerization and decarboxylation of an unsaturated carboxylic acid toproduce an unsaturated organic compound, wherein n is between 0-14 forthe purposes of the figure.

FIG. 4 is a chromatogram of a gas chromatography-mass spectrometry of1-octadecene as a function of elution time (minutes).

FIG. 5 is a chromatogram of a gas chromatography-mass spectrometry of1-octadecene after the isomerization process described in Example 10 asa function of elution time (minutes).

FIG. 6 is a chromatogram of a gas chromatography-mass spectrometry of1-octadecene after the isomerization process described in Example 11 asa function of elution time (minutes).

FIG. 7 is a chromatogram of a gas chromatography-mass spectrometry of1-octadecene after the isomerization process described in Example 11A asa function of elution time (minutes).

FIG. 8 is a chromatogram of a gas chromatography-mass spectrometry of1-octadecene after the isomerization process described in Example 12 asa function of elution time (minutes).

FIG. 9 is a chromatogram of a gas chromatography-mass spectrometry of2-methyl-1-undecene as a function of elution time (minutes), before theisomerization process described in Example 13.

FIG. 10 is a chromatogram of a gas chromatography-mass spectrometry of2-methyl-1-undecene after the isomerization process described in Example13 as a function of elution time (minutes).

FIG. 11 is a chromatogram of a gas chromatography-mass spectrometry ofmethyl-10-undecenoate as a function of elution time (minutes), beforethe isomerization process described in Example 14.

FIG. 12 is a chromatogram of a gas chromatography-mass spectrometry ofmethyl-10-undecenoate, after the isomerization process described inExample 14 as a function of elution time (minutes).

FIG. 13 is a chromatogram of a gas chromatography-mass spectrometry ofmethyl-10-undecenoate after the isomerization process described inExample 15 as a function of elution time (minutes).

FIG. 14 is a chromatogram of a gas chromatography-mass spectrometry ofmethyl 9-octadecenoate after the isomerization process for 4 hours asdescribed in Example 16 as a function of elution time (minutes).

FIG. 15 is a chromatogram of a gas chromatography-mass spectrometry ofmethyl 9-octadecenoate after the isomerization process for 24 hours asdescribed in Example 17 as a function of elution time (minutes).

FIG. 16 is a chromatogram of a gas chromatography-mass spectrometry ofmethyl 9-cis-octadecenoate after the isomerization process for 4 hoursas described in Example 16 as a function of elution time (minutes).

FIG. 17 is a chromatogram of a gas chromatography-mass spectrometry ofmethyl 9-octadecenoate after the isomerization process for 24 hours asdescribed in Example 18 as a function of elution time (minutes).

FIG. 18 is a chromatogram of a gas chromatography-mass spectrometry of10-undecenoic acid after the decarboxylation and isomerization processas described in Example 20 as a function of elution time (minutes).

FIG. 19 is a chromatogram of a gas chromatography-mass spectrometry of10-undecenoic acid after the decarboxylation and isomerization processas described in Example 21 as a function of elution time (minutes).

FIG. 20 is a chromatogram of a gas chromatography-mass spectrometry of10-undecenoic acid after the decarboxylation and isomerization processas described in Example 22 as a function of elution time (minutes).

FIG. 21 is a chromatogram of a gas chromatography-mass spectrometry of10-undecenoic acid after the decarboxylation and isomerization processas described in Example 23 as a function of elution time (minutes).

FIG. 22 is a chromatogram of a gas chromatography-mass spectrometry of10-undecenoic acid after the decarboxylation and isomerization processas described in Example 23 as a function of elution time (minutes).

FIG. 23 is a chromatogram of a gas chromatography-mass spectrometry of10-undecenoic acid after the decarboxylation and isomerization processas described in Example 23 as a function of elution time (minutes).

FIG. 24 is a chromatogram of a gas chromatography-mass spectrometry of10-undecenoic acid after the decarboxylation and isomerization processas described in Example 23 as a function of elution time (minutes).

FIG. 25 is a chromatogram of a gas chromatography-mass spectrometry ofundecanoic acid as described in Example 23A as a function of elutiontime (minutes).

FIG. 26 is a chromatogram of a gas chromatography-mass spectrometry of9-cis-octadecenoic acid after the decarboxylation and isomerizationprocess as described in Example 24 as a function of elution time(minutes).

FIG. 27 is a chromatogram of a gas chromatography-mass spectrometry of9-cis-octadecenoic acid after the decarboxylation and isomerizationprocess as described in Example 25 as a function of elution time(minutes).

FIG. 28 is a chromatogram of a gas chromatography-mass spectrometry of9-cis-octadecenoic acid after the decarboxylation and isomerizationprocess as described in Example 26 as a function of elution time(minutes).

FIG. 29 is a chromatogram of a gas chromatography-mass spectrometry of9-cis-octadecenoic acid after the decarboxylation and isomerizationprocess as described in Example 27 as a function of elution time(minutes).

FIG. 30 is a chromatogram of a gas chromatography-mass spectrometry of9-cis-octadecenoic acid after the decarboxylation and isomerizationprocess as described in Example 28 as a function of elution time(minutes).

FIG. 31 is a chromatogram of a gas chromatography-mass spectrometry of9-cis-octadecenoic acid after the decarboxylation and isomerizationprocess as described in Example 29 as a function of elution time(minutes).

FIG. 32 is a chromatogram of a gas chromatography-mass spectrometry of9-cis-octadecenoic acid after the decarboxylation and isomerizationprocess as described in Example 30 as a function of elution time(minutes).

FIG. 33 is a chromatogram of a gas chromatography-mass spectrometry of9-cis-octadecenoic acid after the decarboxylation and isomerizationprocess as described in Example 31 as a function of elution time(minutes).

FIG. 34 is a chromatogram of a gas chromatography-mass spectrometry of9-cis-octadecenoic acid after the decarboxylation and isomerizationprocess as described in Example 32 as a function of elution time(minutes).

FIG. 35 is a chromatogram of a gas chromatography-mass spectrometry of9-cis-octadecenoic acid after the decarboxylation and isomerizationprocess as described in Example 33 as a function of elution time(minutes).

FIG. 36 is a chromatogram of a gas chromatography-mass spectrometry of9-cis-octadecenoic acid after the decarboxylation and isomerizationprocess as described in Example 34 as a function of elution time(minutes).

FIG. 37 is a chromatogram of a gas chromatography-mass spectrometry of9-cis-octadecenoic acid after the decarboxylation and isomerizationprocess as described in Example 35 as a function of elution time(minutes).

FIG. 38 is a chromatogram of a gas chromatography-mass spectrometry of9-cis-octadecenoic acid after the decarboxylation and isomerizationprocess as described in Example 36 as a function of elution time(minutes).

FIG. 39 is a chromatogram of a gas chromatography-mass spectrometry of9-cis-octadecenoic acid after the decarboxylation and isomerizationprocess as described in Example 37 as a function of elution time(minutes).

FIG. 40 is a chromatogram of a gas chromatography-mass spectrometry of9-cis-octadecenoic acid control as described in Example 37A as afunction of elution time (minutes).

FIG. 41 is a chromatogram of a gas chromatography-mass spectrometry ofR-12-hydroxy-9-cis-octadecenoic acid after the decarboxylation andisomerization process as described in Example 38 as a function ofelution time (minutes).

FIG. 42 is a ¹³C NMR spectra of the reaction as described in Example 38.

FIG. 43 is a chromatogram of a gas chromatography-mass spectrometry ofR-12-hydroxy-9-cis-octadecenoic acid after the decarboxylation andisomerization process as described in Example 39 as a function ofelution time (minutes).

FIG. 44 is a ¹³C NMR spectra of the reaction as described in Example 39.

FIG. 45 is a chromatogram of a gas chromatography-mass spectrometry ofR-12-hydroxy-9-cis-octadecenoic acid control as described in Example 39Aas a function of elution time (minutes).

FIG. 46 is a ¹³C NMR spectra of the control reaction as described inExample 39A.

FIG. 47 is a ¹³C NMR spectra of triolein after the isomerization processas described in Example 40.

FIG. 48 is a ¹³C NMR spectra of the starting material as described inExample 40.

FIG. 49 is a ¹³C NMR spectra of triolein after the isomerization processas described in Example 41.

FIG. 50 is a ¹H NMR spectra of isomerized product after the process asdescribed in Example 42.

FIG. 51 is a ¹H NMR spectra of isomerized product of the startingmaterial for the process as described in Example 42.

FIG. 52 is a ¹H NMR spectra of material after the process as describedin Example 42A.

FIG. 53 is a ¹H NMR spectra of isomerized product after the process asdescribed in Example 43.

FIG. 54 is a ¹H NMR spectra of material after the process as describedin Example 43A.

FIG. 55 is a chromatogram of a gas chromatography-mass spectrometry of9-cis-octadecenoic acid after the decarboxylation and isomerizationprocess as described in Example 44 as a function of elution time(minutes).

FIG. 56 is a chromatogram of a gas chromatography-mass spectrometry of9-cis-octadecenoic acid after the decarboxylation and isomerizationprocess as described in Example 56 as a function of elution time(minutes).

FIG. 57 is a chromatogram of a gas chromatography-mass spectrometry of10-undecenoic acid after the decarboxylation and isomerization processas described in Example 19 as a function of elution time (minutes).

FIG. 58 is a depiction of an exemplar reaction scheme for thepolymerization of an alkene, where the tandem isomerization stem gives adifferent product than the polymerization alone.

FIG. 59 is a ¹H NMR spectrum of the isomerized octadecene from Example10 using the starting material in Example 47.

FIG. 60 is a ¹³C NMR spectrum of the isomerized octadecene from Example10, using the starting material in Example 47.

FIG. 61 is a ¹H NMR spectrum of the polymerized isomerized octadecene ofExample 47.

FIG. 62 is a ¹³C NMR spectrum of the polymerized isomerized octadeceneof Example 47.

FIG. 63 is a GC-MS chromatogram of isomerized tetradecene showing amixture of isomers as a function of elution time (minutes).

FIG. 64 is a GC-MS chromatogram of polymerized isomerized tetradeceneshowing conversion to dimeric product as a function of elution time(minutes).

FIG. 65 is a depiction of an exemplar reaction scheme for thedecarboxylation reaction followed by the self metathesis reaction tomake a plurality of alkene compounds.

FIG. 66 is a GC-FID chromatogram of the self metathesis reaction ofisomerized heptadecene as a function of elution time (minutes) showing amixture of isomers of alkenes of various size.

FIG. 67 is a depiction of an exemplar reaction scheme for thedecarboxylation reaction followed by the cross metathesis with ethene tomake a distribution of α-olefins.

FIG. 68 is a GC-FID chromatogram of the cross metathesis reaction ofisomerized heptadecene as a function of elution time (minutes) showing amixture of isomers of alkenes of various size.

FIG. 69 is a depiction of an exemplar reaction scheme for theisomerization of methyl 9-cis-octadecenoate followed by the crossmetathesis with ethene to make a plurality of alkene and estercompounds.

FIG. 70 is a GC-FID chromatogram of isomerized methyl cis-9-octadeceneafter a metathesis reaction with ethene as a function of elution time(minutes).

DETAILED DESCRIPTION OF THE INVENTION

Definitions

As used in the specification and claims, the singular form “a”, “an” and“the” include plural references unless the context clearly dictatesotherwise.

Hereinafter, the present invention is explained in detail with referenceto the following examples. The examples, however, should not in anysense be interpreted as limiting the scope of the present invention.

As used herein the term “alkene” or “olefin” refers to an unsaturatedcompound containing at least one carbon to carbon double bond. Examplesof such include, but are not limited to any hydrocarbyl, hydrocarbylaromatics, substitute or unsubstituted unsaturated fatty acids,unsaturated fatty esters, triglycerides diol diesters, mono-esters,derivatives of olefins having been reacted under olefin metathesisprocesses such as cross metathesis, ring-opening metathesis,ring-closing metathesis, acyclic diene metathesis or derivatives ofolefins having been polymerized.

As used herein, the term “fatty acid” is to be understood in thisspecification as a long chain carboxylic acid having at least six carbonatoms. Fatty acids may be saturated or unsaturated compounds. Thesecompounds may contain linear or branched alkyl groups, for example,linear or branched alkyl groups having between six and thirty carbonatoms. Preferably fatty acids comprise one or more ethylenicallyunsaturated carbons in the alkyl chain and include hexenoic acid,heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoicacid, undecylenic acid, hendecenoic acid, dodecenoic acid, tridecenoicacid, tetradecenoic acid, myristitoleic acid, myristelaidic acid,pentadecenoic acid, hexadecenoid acid, palmitoleic acid, palmelaidicacid, heptadecenoic acid, octadecenoic acid, petroselinic acid,petroselaidic acid, oleic acid, elaidic acid, vaccenic acid, ricinoleicacid, ricinelaidic acid, nonadecenoic acid, eicosenoic acid, gondolicacid, heneicosenoic acid, docosenoic acid, erucic acid, brassidic acid,tricosenoic acid, tetracosenoic acid, nervonic acid, linoleic acid,lineladic acid, conjugated linoleic acid, linolenic acid, gammalinolenic acid, eicosadienoic acid, homogamma linolenic acid,eicosatrienoic acid, eicosatetranoic acid, arachidonic acid,eicosapentaenoic acid, EPA, docosadienoic acid, docosatrienoic acid,docosatetraenoic acid, docosapentaenoic acid, docosahexaenoic acid, andDHA.

As used herein, the term “fatty acid derivative” is to be understood inthis specification as any compound comprising one or more groups derivedfrom fatty acids. Examples of fatty acid derivatives are salts of fattyacids, for example salts, carboxylate salts, alkali salts, esters offatty acids, preferably fatty acid ester group containing lipids, suchas fatty acid ester group containing glycerolipids, fatty acid estergroup containing glycerophospho-lipids, fatty acid ester groupcontaining sphingolipids, fatty acid ester group containing sterollipids, fatty acid ester group containing prenol lipids, fatty acidester group containing saccharolipids and fatty acid ester groupcontaining polyketides.

Preferred fatty acid derivatives are: octadecenoic acid, cinnamic acid,undecenoic acid, hexadecenoic acid, hydroxy octadecenoic acid.

As used herein, the term “recovering” as used in the context ofrecovering an isomerized product, decarboxylated product, or a tandemisomerized and decarboxylated product includes: crystallization,distillation, reactive distillation, extrusion, decanting, extraction,microfiltration, nanofiltration, or such techniques that are known tothose skilled in the art.

The disclosed process utilizes a metal-based homogeneous orheterogeneous catalyst. As used herein, the term “catalyst precursor” ametal compound where it can be activated in order to be used as acatalyst, particularly as an olefin isomerization or decarboxylationcatalyst. Generally, such catalysts are activated by means of heating asdescribed herein below. In one embodiment, the catalyst precursor formas a catalyst in situ with the process described herein.

The catalyst or catalyst precursors used in the process containruthenium or osmium compounds. It is contemplated that the catalyst orcatalyst precursor contained both ruthenium and osmium would be utilizedfor the disclosed isomerization, decarboxylation, and duel isomerizationdecarboxylation processes.

The selection of a suitable ruthenium or osmium compound to provide thecatalytic activity for isomerization or decarboxylation or tandemisomerization and decarboxylation reaction is not narrowly critical.Essentially any ruthenium or osmium compound can be effectively utilizedto carry out the disclosed isomerization and/or decarboxylationreactions. However, the invention is believed to involve novelruthenium-based catalysts and osmium-based catalysts that promote theisomerization of an olefin and decarboxylation of an unsaturatedcarboxylic acid as the said metal forms a complex with the reactionmixture. It is believed the primary requirement for the generation ofsuch catalysts and the requisite catalytic activity are rutheniumprecursors to the catalyst which can be converted to [Ru(CO)₂RCO₂]_(n)or similar compounds even if the precursor during the reaction fails tobe converted to such structures. [Ru(CO)₂RCO₂]_(n) or similar compoundsmay or may not be the isomerization or decarboxylation catalyst of theinvention but it has been noted that the use of such compounds assuresthe effective catalytic reaction and the results herein characterized.The process of this invention may be practiced with a vast array ofruthenium and/or osmium compounds. Even instances where the ruthenium orosmium compound is too stable for catalyzing the reaction, catalysts canbe effected by including a compound which does not adversely affect theisomerization or decarboxylation reaction and stimulates the rutheniumor osmium compound to be converted to a species having catalyticactivity. For example, ruthenium chloride is a sluggish catalyst but ismade quite active by the addition of an alkali such as an alkali metalsalt of a carboxylic acid, viz. sodium oleate. It is not presumed thatsimple ruthenium salt compounds are the catalyst or that many of theruthenium compounds herein used to effect the catalytic reaction are thecatalyst. The exact ruthenium or osmium containing compound or compoundsthat constitute the catalyst of this invention is not appreciated butwhat is appreciated is that many ruthenium or osmium compounds can beused to in situ generate the catalyst. The diversity of the selection ofruthenium compounds or osmium compounds suitably employable asprecursors to catalysts in the process of the invention is quite broad.It is further contemplated that the catalyst or catalyst precursor isrecovered for subsequent isomerization, decarboxylation, or tandem theisomerization and decarboxylation reactions. It is preferable that thecatalyst or precursor be maintained in an anaerobic atmosphere toprevent oxidation of the catalyst of precursor.

Compounds containing such ruthenium moieties include rutheniumcarboxylates and ruthenium carbonyls such as [Ru(CO)₂Acetate]_(n),Ru₃(CO)₁₂, [Ru(CO)₂(EtCO₂)]_(n), or [Ru_(x)C_(y)O_(z)H_(w)]_(n) where Xis an integer greater or equal to 1, and W, Y, and Z are whole numbersor zero. Other catalyst or catalyst precursor containing rutheniumcompounds include ruthenium carbenes and ruthenium chloride. Thepreferred catalyst and catalyst precursors are Ru₃(CO)₁₂,[Ru(CO)₂(EtCO₂)]_(n), Ru₃O(EtCO₂)_(m)(H₂O)_(n). Catalyst or catalystprecursors containing osmium compounds having a ligand of chloride,carbene, or carboxylate. As used in determining the precursor formula, nand m are integers greater than zero.

It is contemplated that the catalyst compounds may range from supportedmaterial such as ruthenium on carbon, alumina, and the like. Othercontemplated support material includes silica, alumina, zeolites,zirconia, titania, titania, carbon, polyacrylic acid copolymers, acrylicacid containing polymers, and methacrylic acid containing polymers.

The preferred catalysts are formed from ruthenium carbonyl carboxylates,or precursors which can convert into these species. Based on therecognition that ruthenium carbonyl reacts with carboxylic acids toproduce soluble orange-yellow complexes possessing the empirical formula[Ru(CO)₂RCO₂]_(n) and the fact these complexes appear sufficientlylabile to accommodate coordination of alkenyl double bonds andruthenium-bound carboxylates, it is believed that such structures areinvolved in the catalysis of the isomerization and decarboxylationprocess. For example, it is known that in the presence of carbonmonoxide, [Ru(CO)₂RCO₂]_(n) is readily converted to Ru₂(CO)₆(RCO₂)₂dimer. Analogously, substitution with other ligands such as phosphinesgives Ru₂(CO)₄(L)₂(RCO₂)₂ complexes, where L is a donor ligand. Similaraffinity for coordination is thus proposed for alkenyl derivatives.

It is contemplated that compounds containing ruthenium includestetrahydridotetraruthenium dodecacarbonyl, H₄Ru₄ (CO)₁₂, which can alsobe used to form the catalyst.

Catalyst precursors such as ruthenium(III) chloride, ruthenium(III)iodide, tris(2,2-bipyridyl)ruthenium(II) chloride hexahydrate,dichlorotricarbonylruthenium (II) dimer, [RuCl₂(CO)₃]₂, ruthenium (III)acetoacetonate, ruthenium (IV) oxide, ruthenium on carbon, ruthenium onalumina, and ruthenocene are contemplated to exhibit some level ofcatalyst activity.

The olefin isomerization process of this invention using Ru(CO)_(X)compounds may be conducted at temperatures in the range of about 50° C.to about 350° C., but preferably in the range of about 150° C. to about300° C. The isomerization process is typically conducted in an inertatmosphere e.g., under nitrogen, argon or in the presence of other gasessuch as hydrogen, carbon dioxide, carbon monoxide, and ethylene. Theprocess is typically conducted at atmospheric pressure (about 1.0 bars)but may be conducted at any manageable pressure typically in the rangeof about 0.1 to about 25 bars, and preferably in the range of about 0.5bars to about 5.0 bars. The reaction may be carried out at pressureswhich are subatmospheric, atmospheric or superatmospheric. In somesituations, reaction can also be conducted under vacuum such as in adistillation apparatus.

The olefin decarboxylation process of this invention using the empiricalformula Ru(CO)_(X), compounds may be conducted at temperatures in therange of about 90° C. to about 350° C., but preferably in the range ofabout 150° C. to about 300° C. The decarboxylation process is typicallyconducted in an inert atmosphere e.g., under nitrogen, argon or in thepresence of other gases such as hydrogen, carbon dioxide, carbonmonoxide, and ethylene. The process is typically conducted atatmospheric pressure (about 1.0 bars) but may be conducted at anymanageable pressure typically in the range of about 0.1 to about 25bars, and preferably in the range of about 0.5 bars to about 5.0 bars.The reaction may be carried out at pressures which are subatmospheric,atmospheric or superatmospheric. In some situations, reaction can alsobe conducted under vacuum such as in a distillation apparatus.

The dual tandem isomerization and decarboxylation process of thisinvention using Ru(CO)_(X) compounds may be conducted at temperatures inthe range of about 90° C. to about 350° C., but preferably in the rangeof about 150° C. to about 300° C. The isomerization and decarboxylationprocess is typically conducted in an inert atmosphere e.g., undernitrogen or in the presence of other gases such as hydrogen, carbondioxide, carbon monoxide, and ethylene. The process is typicallyconducted at atmospheric pressure (about 1.0 bars) but may be conductedat any manageable pressure typically in the range of about 0.1 to about25 bars, and preferably in the range of about 0.5 bars to about 5.0bars. The reaction may be carried out at pressures which aresubatmospheric, atmospheric or superatmospheric. In some situations,reaction can also be conducted under vacuum such as in a distillationapparatus.

It has been found that [Ru(CO)₂RCO₂]_(n), can be generated in severalways. For example, the trinuclear complex,[Ru₃O(C₂H₅COO)₆(H₂O)₃](C₂H₅COO)] gives an efficient isomerization ordecarboxylation catalyst. Visual color change observations suggest Ru₃O(C₂H₅COO)₆(H₂O)₃](C₂H₅COO) can convert to [Ru(CO)₂RCO₂]_(n) underisomerization or decarboxylation reaction conditions under an argonatmosphere. It is contemplated that generation of the ruthenium complexwould be generated in inert atmospheres such as argon through a redoxreaction. Visual evidence of this reaction observed a green air oxidizedcomplex turning yellow amber following isomerization or decarboxylationcatalysis.

The amount of the ruthenium catalyst useful for effecting theisomerization and/or decarboxylation reaction is not narrowly critical.The typical amount is a catalytically effective amount, that is, anamount which is sufficient to effect the desired isomerization and/ordecarboxylation. For example, it has been established that rutheniumcatalyst concentrations ranging roughly from about 50,000 parts to about0.05 part per million (ppm) ruthenium based on the weight of the liquidphase reaction medium can be used to effect the reaction. It is believedthat larger and smaller amounts of the catalyst may be used to effectthe reaction. The most preferred range is from about 5,000 ppm to about0.5 ppm ruthenium, same basis.

As used herein the term “apparently complete steady state” refers to anobservable amount of isomerized and/or decarboxylated product via gaschromatography, wherein additional time or the addition of catalyst orcatalyst precursor would not result in a change in product distribution.

The following examples set forth methods in accordance with theinvention. It is to be understood, however, that these examples areprovided by way of illustration and nothing therein should be taken as alimitation upon the overall scope of the invention.

Example 1: Isomerization of Oleic Acid with [Ru(CO)₂Acetate]_(n)

2.9 mg of [Ru(CO)₂Acetate]_(n) and 5.10 grams of oleic acid (90% UnitedStates Biochemical Corporation) was charged to a round-bottomed flaskequipped with a stir bar, thermometer, and nitrogen inlet. Thecalculated ruthenium concentration was 270 parts per million. The purgedflask was heated in a sand-bath crucible at 263° C.-277° C. for 1 hour.Upon cooling the flask contents started to cloud and solidify at 31°C.-32° C.

Example 2: Isomerization and Decarboxylation of Oleic Acid

A melted small sample of the flask contents from Example 1 was takenfrom the original reaction mixture by pipette and charged to a smallvial. The vial was flushed with nitrogen and crimped. The sample wasplace on a hot plate. The sample appears to start vaporizing (septumpuffed up). Within about one minute the vial was removed from the heatand allowed to cool. The vial, cooled to room temperature, was a yellowflowing liquid (liquid Analyzed by IR) that eventually solidified.Through this short heating, the melting point was decreased compared tothe prior composition. The vial was again heated on the hot plate whilebeing continuously purged with nitrogen vial a Pasteur Pipette (packedthrough the septum) for a few minutes. The release of a gaseoussubstance was observed using a bubbler. When the vial was cooled to roomtemperature, it resulted in an intensely yellow colored liquid substancethat solidified to a solid overnight. The vial contents was treated withan additional ruthenium in the form of Ru₃(CO)₁₂ (a 1 mg particle) undernitrogen. The vial, equipped with a Pasteur pipette for nitrogendelivery was placed on the hot plate next to a very small beaker filledwith sand and containing the bulb of a high temperature thermometer at260° C. The vial occasionally bubbled as the temperature reached 260° C.The heating lasted approximately 0.7 hr. The cooled vial contained aviscous liquid. IR analysis indicated that the oleic acid was noticeablybeing isomerized and decarboxylated. The carbonyl frequency at 1710 cm⁻¹was decreasing while a weaker olefin band at 1465 cm⁻¹ was increasingrelative to previous IR samples. A small amount of the reaction productwas dissolved in petroleum ether. GC analysis verified isomeric C₁₇olefins products.

Example 3: Decarboxylation of Cinnamic Acid Using Ru₃(CO)₁₂

In a vial, 0.10 grams of trans-cinnamic acid was added to 1.1 mg ofRu₃(CO)₁₂. As a comparative example, a separate vial with 0.10 grams oftrans-cinnamic acid with no ruthenium was prepared.

The vials were flushed with nitrogen, capped with a septum, crimped, andfitted with a Pasteur Pipette (for the introduction of nitrogenatmosphere and the release of gaseous products). The Pipette bulb waspierced with a nitrogen inlet needle to maintain a nitrogen atmosphere.The vials were placed together on a hot plate next to a very smallbeaker filled with sand and containing the bulb of a high temperaturethermometer.

As the hot plate warmed, the Ru₃(CO)₁₂-containing vial melted at a sandbath temperature of 99° C. forming an orange solution initially. As thesand temperature reached 135° C., (hot plate setting 250° C.) theRu₃(CO)₁₂-containing vial started to bubble with the appearance of a“cloudy gas” evolving into the Pipette and then the refluxing of aliquid which condensed in the Pasteur Pipette and returned to the vial.Refluxing on the sides of the vial were also observable. The vialinitially containing ruthenium was heated 20-30 minutes and the sandtemperature increased to 154° C. At a sand temperature of 85° C., thevial with Ru₃(CO)₁₂ solidified to a clear yellow-orange solid with astyrene odor. The vial lost a mass of ˜0.02 grams, indication the lossof CO₂ via decarboxylation.

In the vial where no ruthenium was added, the trans-cinnamic acid meltedat ˜105° C. forming a yellow-green liquid. The vial was heated 20-30minutes and the sand temperature increased to 154° C. Continualapplication of heat did not appear to change the yellow-green liquid.The hot plate was turned off and the vial was allowed to cool. At a sandtemperature of 95° C. the vial containing no ruthenium solidified.

The contents of each vial was dissolve in about 0.2 mL of acetone andanalyzed by gas chromatography. In the vial containing Ru₃(CO)₁₂ showeda relative peak area ratio of 0.708 styrene and 0.292 trans-cinnamicacid. In the vial without ruthenium added, a relative peak area ratio of0.001 styrene:0.999 of trans-cinnamic acid.

Example 4: Isomerization of 10-Undecylenic Acid with Ru₃(CO)₁₂ at 180°C.

10-Undecylenic acid (0.124 grams) and Ru₃(CO)₁₂ (0.7 mg) were added to asmall vial. The vial was flushed with nitrogen, capped, crimped, fittedwith a wire hook, and suspended in an 180° C. oil bath. The reactionmixture was heated several days at a temperature range of 180° C. to185° C. The final solution remained amber orange in color. Occasionally,the vial was removed briefly from the bath for the removal of a GCsample (at times of 5 h, 20 h, 40 h, 116.5 h, and 186 h). Samples werediluted with acetone prior to GC analysis. GC analysis showedprincipally the isomerized undecylenic acid product.

Example 5: Ruthenium-Catalyzed Decarboxylation of Carboxylic Acid UsingRu₃(CO)₁₂

In separate vials the following carboxylic acids were added to vialscontaining the specified masses of Ru₃(CO)₁₂ as indicated in Table 1below. Each vial was flushed with nitrogen, capped and crimped to forman air-tight seal. A copper wire was wrapped around the vial to create asuspension hook and a label was attached. Each assembly was weighedprior to heating.

TABLE 1 Carboxylic Acid Ruthenium Complex 0.0981 grams of trans-cinnamicacid 1.8 mg of Ru₃(CO)₁₂ (MP 133-134° C.) 0.1094 grams of maleic acid(MP 140- 1.4 mg of Ru₃(CO)₁₂ 142° C.) 0.1006 grams of benzoic acid (122-1.8 mg of Ru₃(CO)₁₂ 123° C.)

Example 5A: Decarboxylation of Trans-Cinnamic Acid

The vial was fitted with a nitrogen inlet needle attached to a bubblerand suspended in an oil bath at 127° C. The bath was gradually warmedand the mixture melted forming an orange solution. The nitrogen bubblerate was calibrated in an effort to detect the evolution of productgases from the vial such as carbon dioxide. The temperature of the oilbath was increased to 215° C. (gaseous bubbles, and some refluxing of amore volatile liquid could be seen in the vial). After approximately 30minutes at 215° C. the vial was removed from the oil bath, the solutionwas bright red in color while still hot. The mass loss from the vial was0.0291 grams.

Example 5B: Decarboxylation of Maleic Acid

The vial was fitted with a nitrogen inlet needle attached to a bubblerand suspended in an oil bath at 163° C. The mixture melted but aninsoluble residue was apparent (possibly isomerization to fumaric acid).The nitrogen bubble rate was calibrated in an effort to detect theevolution of product gases from the vial such as carbon dioxide. Thetemperature of the oil bath was increased to 195° C. (gaseous bubbles,and some refluxing of a more volatile liquid could be seen in the vial).After approximately 15 minutes at 190-196° C. the vial was removed fromthe oil bath, the solution was bright red in color while still hot. Themass loss from the vial was 0.0310 grams.

Example 5C: Decarboxylation of Benzoic Acid

The vial was fitted with a nitrogen inlet needle attached to a bubblerand suspended in an oil bath at 165° C. The bath was gradually warmedand the mixture immediately melted forming an orange solution. Thenitrogen bubble rate was calibrated in an effort to detect the evolutionof product gases from the vial such as carbon dioxide. The temperatureof the oil bath was increased to 220° C. After approximately 15 minutesat 215° C.-220° C. the vial was removed from the oil bath, the solutionwas bright red in color while still hot, but solidified to a yellowsolid. The mass loss was not detectable from the vial during thereaction.

Example 6: Decarboxylation of 10-Undecylenic Acid

The vial was charged with Ru₃(CO)₁₂ (2.1 mg) and 10-Undecylenic Acid(0.1636 g), flushed with nitrogen, capped, crimped, and fitted with anitrogen inlet needle that was attached to a bubbler. The sample waswarmed on a hot plate warmed to 280° C.-300° C. for 1 hour. As thereaction progressed, gas evolution and the condensation (refluxing) of avolatile liquid above the burnt orange catalyst solution was observed.When the vial was removed from the heat source, immediately turned alighter amber color. The weight loss during the reaction was 0.0263grams or 16.08%. For total conversion of 10-undecylenic acid (Mw 184.28)to decene isomer(s) (Mw 140.27) the expected mass loss would be 23.9%.GC Analysis confirmed that decene isomers and undecylenic acid isomerswere formed.

Example 7: Decarboxylation of Oleic Acid

The vial was charged with Ru₃(CO)₁₂ (3.3 mg) and oleic acid (0.2109 g),flushed with nitrogen, capped, crimped, and fitted with a nitrogen inletneedle that was attached to a bubbler. The sample was heated on a hotplate warmed to 280° C.-300° C. for 1 hour. The weight loss during thereaction was 0.0351 grams or 16.64%.

Example 8: Decarboxylation of Linoleic Acid

The vial was charged with Ru₃(CO)₁₂ (2.3 mg) and linoleic acid (0.1733g), flushed with nitrogen, capped, crimped, and fitted with a nitrogeninlet needle that was attached to a bubbler. The sample was heated on ahot plate warmed to 280° C.-300° C. for 1 hour. The weight loss duringthe reaction was 0.0075 grams.

Example 9: Decarboxylation of Stearic Acid

The vial was charged with Ru₃(CO)₁₂ (1.9 mg) and stearic acid (0.2277g), flushed with nitrogen, capped, crimped, and fitted with a nitrogeninlet needle that was attached to a bubbler. The sample was heated on ahot plate warmed to 280° C.-300° C. for 1 hour. The weight loss duringthe reaction was 0.0027 grams.

Example 10: The Isomerization of 1-Octadecene with the Reaction Preparedin an Inert-Atmosphere Dry-Box

Inside an inert atmosphere dry-box, 4.9834 g of 1-octadecene, 0.0519 goctadecanoic acid, and 0.003 g Ru₃(CO)₁₂ were weighed into a Pyrex16×150 mm culture tube which was sealed with and a septa capped lid. Thetube was removed from the dry-box and connected to argon flow from aSchlenk line through a 22 gauge needle. The tube was heated in analuminum block which was set to achieve a temperature of 250° C., andreacted for 4 hours. The actual reaction temperature varied withsubstrate and production as some of the reactants and products refluxunder these conditions which can cool the reaction tube. The reactionturned pale yellow, and was analyzed by GC-MS. The GC-MS utilized was anAgilent 7890A gas chromatograph equipped with a 7683B series injectorand a 5975 C quadrapole mass detector. A J&W 123-3832, 30 m×320 um×0.25um, column was used. Injections were 1 uL and a 50:1 split ratio wasused. Temperatures were: MS Source 230° C., MS Quad 150° C., GC inlet340° C., GC Auxiliary line 340° C. The oven temperature program was: 40°C. hold 3 min, ramp 10° C./min to 190° C. hold 5 min, ramp 25° C./min to340° C. Samples of ˜10 uL were dissolved in 1 mL of acetone foranalysis, and response factors were calculated by injection of knowncompounds using the same method. The starting material, FIG. 4 and theproduct, FIG. 5, depict the effect of the isomerization.

Example 11: Isomerization of 1-Octadecene with [Ru(CO)₂(EtCO₂)]_(n)

This reaction was performed identically to Example 10, but in this case,2.0017 g of 1-octadecene and 0.002 g [Ru(CO)₂(EtCO₂)]_(n) were used.This reaction solution turned orange, then brown. The chromatogram, FIG.6, has a similar distribution to that in Example 10.

Example 11a Control Experiment Isomerization with No Ruthenium CatalystPrecursor

This was reaction was performed identically to Example 10, but in thiscase, 5.0519 g of 1-octadecene, but no stearic acid or Ru₃(CO)₁₂ wereused. The chromatogram, FIG. 7, is much less isomerized than in Example10.

Example 12: Isomerization without the Presence of Octadecanoic Acid

This was reaction was performed identically to Example 10, but in thiscase, 5.0519 g of 1-octadecene and 0.043 g Ru₃(CO)₁₂. No octadecanoicacid was used and the reaction temperature was only 150° C. Thechromatogram, FIG. 8, has a similar distribution to that in Example 10.

Example 13: Isomerization of 2-Methyl-1-Undecene withRu₃(CO)₁₂/Octadecanoic Acid

A stock solution of catalyst precursor was made, inside an inertatmosphere dry-box, by melting 5.0382 g of octadecanoic acid and adding0.0010 g Ru₃(CO)₁₂. This solution was heated to 100° C. for 45 minutes,upon which time the solution turned orange. Upon cooling a yellowsolution could be observed, which solidified at room temperature. Insideof the dry-box, 0.0674 g of catalyst precursor stock solution was addedto 0.9387 g of 2-methyl-1-undecenoene in a speta capped pyrex culturetube. This tube was taken out of the dry-box, connected by needle to anargon flow via Schlenk line, and heated to 200° C. for 4 hours. Thissample was analyzed by GC-MS, as done in Example 10. Comparison of thechromatograms, FIGS. 9 and 10, show 14% conversion to the2-methyl-2-undecene.

Example 14: Isomerization of Methyl 10-Undecenoate with[Ru(CO)₂(EtCO₂)]_(n) in 4 Hours

This reaction was ran by the same method as Example 10, using 0.0021 gof [Ru(CO)₂(EtCO₂)]_(n) and 2.0521 g of methyl 10-undecenoate. Thisreaction was run at 250° C. for 4 hours. Comparison of thechromatograms, FIGS. 11 and 12, show apparently complete steady stateisomerization.

Example 15: Isomerization of Methyl 10-Undecenoate with[Ru(CO)₂(EtCO₂)]_(n) in 4 Hours at 150° C.

This reaction was ran by the same method as Example 10, using 0.0028 gof [Ru(CO)₂(EtCO₂)]_(n) and 2.0095 g of methyl 10-undecenoate. Thisreaction was run at 150° C. for 4 hours. The GC-MS of the product, FIG.13, shows only a small amount of isomerization where only ˜4 isomerswere observable.

Example 16: Isomerization of Methyl 9-Cis-Octadecenoate with[Ru(CO)₂(EtCO₂)]_(n) in 4 Hours

This reaction was ran by the same method as Example 10, using 0.0026 gof [Ru(CO)₂(EtCO₂)]_(n) and 2.0013 g of methyl 9-cis-octadecenoate. Thisreaction was run at 250° C. for 4 hours. The GC-MS of the product, FIG.14, shows apparently complete steady state isomerization. The GC-MS ofthe product, FIG. 16, shows partial isomerization with reaction at 150°C. for 4 hours.

Example 17: Isomerization of Methyl 9-Cis-Octadecenoate with[Ru(CO)₂(EtCO₂)]_(n) in 24 Hours

This reaction was ran by the same method as Example 10, using 0.0024 gof [Ru(CO)₂(EtCO₂)]_(n) and 2.0061 g of methyl 9-cis-octadecenoate. Thisreaction was run at 250° C. for 4 hours. The GC-MS of the product, FIG.15, shows apparently complete steady state isomerization.

Example 18: Isomerization of Methyl 9-Cis-Octadecenoate with[Ru(CO)₂(EtCO₂)]_(n) in 24 Hours at 150° C.

This reaction was ran by the same method as Example 10, using 0.0031 gof [Ru(CO)₂(EtCO₂)]_(n) and 2.0109 g of methyl 9-cis-octadecenoate. Thisreaction was run at 150° C. for 24 hours. The GC-MS of the product, FIG.17, shows only a small amount of isomerization where only 2 isomers wereobserved.

Example 19: The Decarboxylation and Isomerization of 10-Undecenoic Acidwith [Ru(CO)₂(EtCO₂)]_(n) at 250° C. for 4 Hours

This reaction was ran by the same method as Example 10, using 0.0021 gof [Ru(CO)₂(EtCO₂)]_(n) and 2.0460 g of 10-undecenoic acid. Thisreaction was run at 250° C. for 4 hours. The GC-MS chromatogram, FIG.57, shows apparently complete steady state isomerization and alkeneproduction of ˜2%.

Example 20: The Decarboxylation and Isomerization of 10-Undecenoic Acidwith [Ru(CO)₂(EtCO₂)]_(n) at 250° C. for 24 Hours

This reaction was ran by the same method as Example 10, using 0.0028 gof [Ru(CO)₂(EtCO₂)]_(n) and 2.0437 g of 10-undecenoic acid. Thisreaction was run at 250° C. for 24 hours. The GC-MS chromatogram, FIG.18, shows apparently complete steady state isomerization and alkeneproduction of ˜11%.

Example 21: The Decarboxylation and Isomerization of 10-Undecenoic Acidwith Os₃(CO)₁₂ at 250° C. for 4 Hours

A stock solution was made by the same method as Example 10 using 0.0195g Os₃(CO)₁₂ and 5.0086 g 10-undecenoic acid. Inside an inert atmospheredry-box, an aliquot of this stock solution, 0.5454 g was reactedcombined with an additional 0.5057 g of 10-undecanoic acid in a septacapped 16×150 mm culture tube. This tube was removed from the dry-boxand heated to 250° C. under an argon flow from a Schlenk line, for 2hours, resulting in a pale yellow solution. The actual reactiontemperature varied with substrate and production as some of thereactants and products reflux under these conditions which can cool thereaction tube. The GC-MS chromatogram of the product, FIG. 19, shows˜12% alkene production.

Example 22: The Decarboxylation and Isomerization of 10-Undecenoic Acidwith Os₃(CO)₁₂ at 250° C. for 24 Hours

The method for this reaction was identical to Example 10, using 0.6017 gstock solution, 0.5454 g additional 10-undecenoic acid. This product wasbright yellow, and its GC-MS chromatogram, FIG. 20, shows ˜21% alkeneproduction.

Example 23: The Decarboxylation and Isomerization of 10-Undecenoic Acidwith Ru₃(CO)₁₂ Ran Over Multiple Days, with Added Eicosane, in aReactive Distillation

Inside of an inert atmosphere dry-box, 7.9091 g 10-undecenoic acid,0.2296 g Ru₃(CO)₁₂ and 12.1056 g eicosane were added to a 50 mL roundbottomed flask. The flask was attached to a condenser and the apparatuswas removed from the dry-box and connected to a distillation head. ASchlenk flask was used as a receiver so samples could be taken withminimal exposure to air. Argon flow was connected to the still through aSchlenk line, and the reaction heated with an aluminum block on ahotplate, to ˜250° C. Glass wool was packed around the condenser asnecessary to control reflux vs. distillation rate. After 4 hours, a1.6812 g fraction collected, analyzed by GC-MS, FIG. 21, and confirmedto be completely alkene and eicosane. The still was allowed to coolovernight under argon. The following day, an additional 2.2968 g ofalkene was collected, FIG. 22, and the reactor was allowed to cool and2.2360 g of fresh 10-undecenoic acid was added to the vessel which wasleft overnight under argon. Further fractions of alkene were collectedon days 3 and 4, FIG. 23 and FIG. 24, respectively, between which,0.6052 g of fresh 10-undecenoic acid was added. Overall, a total of 4.53g of alkene was collected, and the 10-undecenoic acid in the reactionpot was isomerized to an apparently complete steady state.

Example 23a Control Experiment The Reaction of a Saturated Fatty Acid,Undecanoic Acid with Ru₃(CO)₁₂ at 250° C. for 4 Hours

This reaction was run by the method in Example 10. A mass of 1.0633 g ofundecanoic acid was used with 0.0095 g Ru₃(CO)₁₂. As an internalstandard, 0.1982 g of pentadecane was also added to the reaction. Theresultant GC-MS, FIG. 25, shows no reaction products were produced inany quantity over 1%.

Example 24: The Decarboxylation and Isomerization of 9-Cis-OctadecenoicAcid with [Ru(CO)₂(EtCO₂)]_(n) at 250° C. for 4 Hours

This reaction was ran by the same method as Example 10, using 0.0020 gof [Ru(CO)₂(EtCO₂)]_(n) and 2.0534 g of 9-cis-octadecenoic acid. Thisreaction was run at 250° C. for 4 hours. The GC-MS chromatogram, FIG.26, shows apparently complete steady state isomerization and alkeneproduction of nearly 50%.

Example 25: The Decarboxylation and Isomerization of 9-Cis-OctadecenoicAcid with [Ru(CO)₂(EtCO₂)]_(n) at 250° C. for 24 Hours

This reaction was ran by the same method as Example 10, using 0.0029 gof [Ru(CO)₂(EtCO₂)]_(n) and 2.0134 g of 9-cis-octadecenoic acid. Thisreaction was run at 250° C. for 24 hours. The GC-MS chromatogram, FIG.27, shows apparently complete steady state isomerization and nearlycomplete alkene production.

Example 26: The Decarboxylation and Isomerization of 9-Cis-OctadecenoicAcid with Ru₃O(EtCO₂)_(m)(H₂O)_(n) at 250° C. for 4 Hours

This reaction was ran by the same method as Example 10, using 0.0024 gof Ru₃O(EtCO₂)_(m)(H₂O)_(n) and 2.0155 g of 9-cis-octadecenoic acid.This reaction was run at 250° C. for 4 hours. The GC-MS chromatogram,FIG. 28, shows apparently complete steady state isomerization and alkeneproduction of ˜12%.

Example 27: The Decarboxylation and Isomerization of 9-Cis-OctadecenoicAcid with Ru₃O(EtCO₂)_(m)(H₂O)_(n) at 250° C. for 24 Hours

This reaction was ran by the same method as Example 10, using 0.0026 gof Ru₃O(EtCO₂)_(m)(H₂O)_(n) and 2.0038 g of 9-cis-octadecenoic acid.This reaction was run at 250° C. for 24 hours. The GC-MS chromatogram,FIG. 29, shows apparently complete steady state isomerization and alkeneproduction of ˜22%.

Example 28: The Decarboxylation and Isomerization of 9-Cis-OctadecenoicAcid with Ru₃(CO)₁₂ at 250° C. for 4 Hours

A stock solution was made by the same method as Example 10 using 0.0128g Ru₃(CO)₁₂ and 5.0102 g 9-cis-octadecenoic acid. Inside an inertatmosphere dry-box, an aliquot of this stock solution, 0.5023 g wasreacted combined with an additional 0.5085 g of 9-cis-octadecenoic acidin a septa capped 16×150 mm culture tube. This tube was removed from thedry-box and heated to 250° C. under an argon flow from a Schlenk line,for 4 hours, resulting in a pale yellow solution. The GC-MS chromatogramof the product, FIG. 30, shows ˜28% alkene production.

Example 29: The Decarboxylation and Isomerization of 9-Cis-OctadecenoicAcid with Ru₃(CO)₁₂ at 250° C. for 24 Hours

The method for this reaction was identical to Example 10, using 0.5028 gstock solution, 0.5061 g additional 9-cis-octadecenoic acid. Thisproduct was bright yellow, and its GC-MS chromatogram, FIG. 31, shows˜45% alkene production.

Example 30: The Decarboxylation and Isomerization of 9-Cis-OctadecenoicAcid with Os₃(CO)₁₂ at 250° C. for 4 Hours

A stock solution was made by the same method as Example 10 using 0.0165g Os₃(CO)₁₂ and 5.0086 g 9-cis-octadecenoic acid. Inside an inertatmosphere dry-box, an aliquot of this stock solution, 0.5013 g wasreacted combined with an additional 0.5345 g of 9-cis-octadecenoic acidin a septa capped 16×150 mm culture tube. This tube was removed from thedry-box and heated to 250° C. under an argon flow from a Schlenk line,for 4 hours, resulting in a pale yellow solution. The GC-MS chromatogramof the product, FIG. 32, shows ˜28% alkene production.

Example 31: The Decarboxylation and Isomerization of 9-Cis-Octadecenoicwith Os₃(CO)₁₂ at 250° C. for 24 Hours

The method for this reaction was identical to Example 10, using 0.5379 gstock solution, 0.5180 g additional 9-cis-octadecenoic acid. Thisproduct was bright yellow, and its GC-MS chromatogram, FIG. 33, shows˜45% alkene production.

Example 32: The Decarboxylation and Isomerization of 9-Cis-OctadecenoicAcid with Benzylidene-Bis(Tricyclohexylphosphine)Dichlororuthenium,Grubbs Generation I, at 250° C. for 4 Hours

This reaction was ran by the same method as Example 10, using 0.0021 gof Grubbs Generation 1, and 2.0349 g of 9-cis-octadecenoic acid. In thisinstance, the Grubbs catalyst is used as a precursor for thedecarboxylation and isomerization reaction and not as a metathesiscatalyst. This reaction was run at 250° C. for 4 hours. The GC-MSchromatogram, FIG. 34, shows apparently complete steady stateisomerization and alkene production of ˜1%.

Example 33: The Decarboxylation and Isomerization of 9-Cis-OctadecenoicAcid with Benzylidene-Bis(Tricyclohexylphosphine)Dichlororuthenium,Grubbs Generation I, at 250° C. for 24 Hours

This reaction was run by the same method as Example 10, using 0.0024 gof Grubbs Generation I, and 2.0603 g of 9-cis-octadecenoic acid. In thisinstance, the Grubbs catalyst is used as a precursor for thedecarboxylation and isomerization reaction and not as a metathesiscatalyst. This reaction was run at 250° C. for 24 hours. The GC-MSchromatogram, FIG. 35, shows apparently complete steady stateisomerization and alkene production of ˜9%.

Example 34: The Decarboxylation and Isomerization of 9-Cis-OctadecenoicAcid with Bis(Tricyclohexylphosphine)Isopentenylidene Dichlororuthenium,at 250° C. for 4 Hours

This reaction was ran by the same method as Example 10, using 0.0018 gof Bis(tricyclohexylphosphine)isopentenylidene dichlororuthenium, and2.0208 g of 9-cis-octadecenoic acid. This reaction was run at 250° C.for 4 hours. In this instance, the Grubbs catalyst is used as aprecursor for the decarboxylation and isomerization reaction and not asa metathesis catalyst. The GC-MS chromatogram, FIG. 36, shows apparentlycomplete steady state isomerization isomerization and alkene productionof greater than 1%.

Example 35: The Decarboxylation and Isomerization of 9-Cis-OctadecenoicAcid with Bis(Tricyclohexylphosphine)Isopentenylidene Dichlororuthenium,at 250° C. for 24 Hours

This reaction was ran by the same method as Example 10, using 0.0030 gof Bis(tricyclohexylphosphine)isopentenylidene dichlororuthenium, and2.0640 g of 9-cis-octadecenoic acid. In this instance, the Grubbscatalyst is used as a precursor for the decarboxylation andisomerization reaction and not as a metathesis catalyst. This reactionwas run at 250° C. for 24 hours. The GC-MS chromatogram, FIG. 37, showsapparently complete steady state isomerization isomerization and alkeneproduction of ˜5%.

Example 36: The Decarboxylation and Isomerization of 9-Cis-OctadecenoicAcid with RuCl₃, at 250° C. for 4 Hours

This reaction was ran by the same method as Example 10, using 0.0018 gof RuCl₃, and 2.0229 g of 9-cis-octadecenoic acid. This reaction was runat 250° C. for 4 hours. The GC-MS chromatogram, FIG. 38, showsapparently complete steady state isomerization and alkene production of˜1%.

Example 37: The Decarboxylation and Isomerization of 9-Cis-OctadecenoicAcid with RuCl₃, at 250° C. for 24 Hours

This reaction was ran by the same method as Example 10, using 0.0027 gof RuCl₃, and 2.0139 g of 9-cis-octadecenoic acid. This reaction was runat 250° C. for 24 hours. The GC-MS chromatogram, FIG. 39, showsapparently complete steady state isomerization and alkene production of˜3%.

Example 37a Control Experiment The Decarboxylation and Isomerization of9-Cis-Octadecenoic Acid without Catalyst, at 250° C. for 24 Hours

This reaction was run by the same method as Example 10. Using 2.0816 gof 9-cis-octadecenoic acid, but no catalysis. GC-MS chromatogram, FIG.40, shows no significant alkene production.

Example 38: The Transformation of R-12-Hydroxy-9-Cis-Octadecenoic Acidwith Ru₃(CO)₁₂ at 250° C. for 4 Hours

Inside of the inert atmosphere dry-box, a saturated solution ofRu₃(CO)₁₂ was made by adding 0.0198 g of Ru₃(CO)₁₂ to 10.0157 gR-12-hydroxy-9-cis-octadecenoic acid. This was heated to 100° C. withstirring for 90 minutes. Excess Ru₃(CO)₁₂ was observed in the yellowsolution. A 1.1386 g aliquot was removed, placed in a septa-cappedculture tube, and was heated according to the method of Example 10, for4 hours. The resultant GC-MS chromatogram, FIG. 41 and ¹³C NMR, FIG. 42,show a variety of products, including the described ketone.

Example 39: The Transformation of R-12-Hydroxy-9-Cis-Octadecenoic Acidwith Ru₃(CO)₁₂ at 250° C. for 24 Hours

This reaction was performed by the method of Example 38. A mass of1.0380 g of the saturated solution was heated for 24 hours. As before,the GC-MS, shows multiple products, FIG. 43 and the ¹³C NMR spectrum,FIG. 44, confirms a ketone is observed.

Example 39a Control Experiment: The Transformation ofR-12-Hydroxy-9-Cis-Octadecenoic Acid without Catalyst at 250° C. for 24Hours

A 1.0224 g sample of R-12-hydroxy-9-cis-octadecenoic acid was heated to250° C., by the method of Example 38. Although the GC-MS chromatogramshows multiple products, FIG. 45, the absence of ketone is confirmed byNMR spectroscopy, FIG. 46.

Example 40: Isomerization of Triolein with [Ru(CO)₂(EtCO₂)]_(n) in 4Hours

This reaction was ran by the same method as Example 10, using 0.0026 gof [Ru(CO)₂(EtCO₂)]_(n) and 1.9896 g of triolein. This reaction was runat 250° C. for 4 hours. The ¹³C NMR spectrum of the product, FIG. 47,shows isomerization of the product, when compared to the spectrum of thestarting material, FIG. 48.

Example 41: Isomerization of Triolein with [Ru(CO)₂(EtCO₂)]_(n) in 24Hours

This reaction was ran by the same method as Example 10, using 0.0026 gof [Ru(CO)₂(EtCO₂)]_(n) and 2.0436 g of triolein. This reaction was runat 250° C. for 24 hours. The C¹³ NMR spectrum of the product, FIG. 49,shows apparently complete steady state isomerization.

Example 42: Isomerization of Soybean Oil with [Ru(CO)₂(EtCO₂)]_(n) in 24Hours

A stock solution of 15.0236 g of soybean oil with 0.0063 g of[Ru(CO)₂(EtCO₂)]_(n) was prepared in an inert atmosphere glovebox as inthe method of Example 38. This reaction was run by the same method asExample 10, using 1.9632 g of soybean oil, at 125° C. for 24 hours. The¹H NMR spectrum of the product, FIG. 50, is similar to the spectrum ofthe starting material, FIG. 51.

Example 42a Control Experiment Isomerization of Soybean Oil without thePresence of Ruthenium

This reaction was run by the same method as Example 10, with 2.1463 g ofsoybean oil, without catalyst precursor. This reaction was run at 125°C. for 24 hours. The ¹H NMR spectrum of the product, FIG. 52, shows verylittle isomerization of the product, when compared to the spectrum ofthe starting material, FIG. 51.

Example 43: Isomerization of Soybean Oil with [Ru(CO)₂(EtCO₂)]_(n) in 24Hours

This reaction was ran by the same method as Example 42, using 2.0137 gof soybean oil solution with [Ru(CO)₂(EtCO₂)]_(n). This reaction was runat 175° C. for 24 hours. The ¹H NMR spectrum of the product, FIG. 53,shows isomerization of the product, when compared to the spectrum of thestarting material, FIG. 51.

Example 43a Control Experiment: Isomerization of Soybean Oil without thePresence of Ruthenium

This reaction was run by the same method as Example 10, with 1.9989 g ofsoybean oil, without catalyst precursor. This reaction was run at 175°C. for 24 hours. The ¹H NMR spectrum of the product, FIG. 54, shows verylittle isomerization of the product, when compared to the spectrum ofthe starting material, FIG. 51.

Example 44: The Decarboxylation and Isomerization of 9-Cis-OctadecenoicAcid with a Mixture of Os₃(CO)₁₂ and Ru₃(CO)₁₂, at 250° C. for 4 Hours

This reaction was ran by the same method as Example 10, using 0.0017 gof Ru₃(CO)_(12n), 0.0011 g Os₃(CO)₁₂, and 2.0436 g of 9-cis-octadecenoicacid. This reaction was run at 250° C. for 4 hours. The GC-MSchromatogram, FIG. 55, shows alkene production of nearly 30%.

Example 45: The Decarboxylation and Isomerization of 9-Cis-OctadecenoicAcid with a Mixture of Os₃(CO)₁₂ and Ru₃(CO)₁₂, at 250° C. for 24 Hours

This reaction was ran by the same method as Example 10, using 0.0017 gof Ru₃(CO)_(12n), 0.0011 g of Os₃(CO)₁₂, and 2.0436 g of9-cis-octadecenoic acid. This reaction was run at 250° C. for 24 hours.The GC-MS chromatogram, FIG. 56, shows alkene production of nearly 80%.

Example 46: Larger Scale Isomerization and Decarboxylation of Oleic Acid

Inside an inter atmosphere dry-box, 0.501 g (0.00078 mol) of Ru₃(CO)₁₂was mixed with 60.1 g (0.21 mol) of 9-cis-octadecenoic acid in a 500 mLroundbottom flask. The mixture was heated to 90° C. for 45 minutes, thena Vigreux column was placed on the flask, which was septa capped, and itwas brought out of the glovebox, and connected to a Schlenk line withargon flow. The flask was placed in a fitted heating block on a hotplatewhich was set to 300° C., corresponding to a reaction temperature of˜280° C. The flask was covered with glass wool and foil, and therefluxing continued for 24 hours, resulting in a dark orange solution.Upon cooling, the crude product was a light yellow solid, which waspurified through vacuum distillation. A still head was attached to theroundbottom flask, and connected to a vacuum showing a pressure readingbelow 0.2 torr. The distillation was monitored and hotplate settingsbetween 150-165° C. gave an overhead temperature recorded between 90-95°C. The final collected product was a clear liquid, (20.9 g, 0.877 mol,42%). GC analysis showed complete the product to be a mixture of isomersof heptadecene.

Example 47: Polymerization of Isomerized Alkenes Using HexafluoroAntimonic Acid

Oligomerization of a sample of isomerized octadecene, made by the methodof Example 11, was carried out in a 50 mL autoclave reactor from ParrInstrument Co. (Moline, Ill.). The reactor was attached to an Isco Model260D high pressure syringe pump used to fill the reactor with CO₂. Inthe reaction, 10 g of octadecene was added to the reactor, which wasthen sealed and purged with N₂ was for 5 minutes before addition of CO₂to the desired pressure and temperature maintained by a Parr 4843controller. Once the reactor was brought to the appropriate temperature,60° C., and pressure of 1200 psi, HSbF₆ was charged into an injectionport to give a molar ratio of catalyst to alkene of 1:1. A flush offresh CO₂ was pumped through the injector line to insure that theinitiator was supplied to the reactor. After reaction of 24 hr, 2 ml ofH₂O was added into reactor to quench any remaining initiator. Theproduct was dissolved in 20 mL hexane and washed sequentially with H₂O,5% aqueous sodium bicarbonate, and H₂O. The hexane solution was driedover sodium sulfate, filtered, and evaporated under reduced pressure. Acomparison of the NMR analysis of the starting material, FIGS. 59 and60, with that of the product, FIGS. 61 and 62, show the apparentlycomplete reaction of the alkene groups. The analysis results as well asthose of gel permeation chromatography show that the dominateconstituent of the material is dimeric, with a small amount of trimerbut no higher oligomers.

Example 48: Isomerization and Polymerization of Isomerized AlkenesHeterogeneous Catalysts

Inside of the inert atmosphere dry-box, 0.0015 g [Ru(CO)₂(EtCO₂)]_(n)was added to 10.0013 g of 7-trans-tetradecene inside a roundbottomflask. It was attached to a Schlenk line and placed in a heating blockon a hotplate set to 250° C. for 4 hours. At this point, isomerizationwas not complete, and additional [Ru(CO)₂(EtCO₂)]_(n), 0.0018 g, wasadded, with heat again applied for 4 hours. A GC-MS trace showed anapparent steady state of isomers. This was checked by heating thereaction again and observing that there was no change in isomerdistribution. The alkene was dried over 4A and 13× mol sieves for atleast 12 hours before performing polymerization reactions. These werealso prepared inside of the inert atmosphere dry-box. Isomerizedtetradecene, 0.1799 g was placed in 16 mm×150 mm test tube. Thecatalyst, sulfated zirconia, 0.0176 g, that had been prepared vialiterature methods, was added. The tube was sealed with a septa cap andattached to a Schlenk line via a needle and placed in a heating block ona hotplate. The polymerization reactions were done at 200 for 4 hours.Comparison of the GC-MS chromatograms of the starting material, FIG. 63,with the product, FIG. 64, show 58% conversion to dimeric material. Acomparison of ¹H NMR spectra shows the alkane/alkene ratio increasesfrom 14.1 to 29.7 in the product.

Example 49: Polymerization of Isomerized Heptadecene Made fromDecarboxylation of 9-Cis-Octadecenoic Acid

This Example was done by the same method as Example 48, exceptisomerized heptadecene from Example 46 was used. It was ran through anAmberlite IRA 400 column and distilled 3 times prior to use.Heptadecene, 0.2296 g, was used with 0.0226 g of sulfated zirconiacatalyst. A comparison of ¹H NMR spectra shows the alkane/alkene ratioincreases from 21.18 to 25.65 in the product.

The sulfated zirconia was prepared as disclosed in Oh J., et al., (2013)Appl Catal. A: Gen., 455, 164-171 and incorporated herein by reference.Namely, five grams zirconium isopropoxide was suspended in 20 mln-propanol with vigorous stirring. Subsequently, 15 ml of a 0.5 Msulfuric acid solution was added dropwise over a period of 30 min. Theresulting gel was stirred overnight, collected by filtration, washedwith water and methanol, then dried under vacuum at 90° C. The resultingsolid was calcined at 625° C. for 2 hr. Scanning Electron Microscopeequipped with an Energy Dispersive Spectrometer indicated the productwas 75.7 wt % Zr, 1.1 wt % S.

Example 50: Polymerization of Isomerized Heptadecene Made fromDecarboxylation of 9-Cis-Octadecenoic Acid, at 250° C., 5 Weight %Catalyst

This example was done by the same method as Example 49, with atemperature of 250° C. Heptadecene, 0.3483 g was used with 0.0173 g ofsulfated zirconia catalyst. A comparison of ¹H NMR spectra shows thealkane/alkene ratio increases from 21.18 to 28.97 in the product.

Example 51: Polymerization of Isomerized Heptadecene Made fromDecarboxylation of 9-Cis-Octadecenoic Acid, at 250° C.

This Example was done by the same method as Example 49, with atemperature of 250° C. Heptadecene, 0.3295 g was used with 0.0328 g ofsulfated zirconia catalyst. A comparison of ¹H NMR spectra shows thealkane/alkene ratio increases from 21.18 to 48.44 in the product.

Example 52: Polymerization of Isomerized Heptadecene Made fromDecarboxylation of 9-Cis-Octadecenoic Acid, at 250° C.

This Example was done by the same method as Example 49, with atemperature of 250° C. Heptadecene, 0.2961 g was used with a differentcatalyst of 0.0228 g of beta zeolite. The beta zeolite catalyst(Zeolyst) was activated by heating at 600° C. for 4 hours. A comparisonof ¹H NMR spectra shows the alkane/alkene ratio increases from 21.18 to28.01 in the product.

As a control, polymerization at a temperature of 250° C. was conductedwith 0.2509 g heptadecene with no added catalyst. A comparison of ¹H NMRspectra shows the alkane/alkene ratio didn't significantly change, 21.18in the starting material and 20.05 in the product.

Example 53: A Self Metathesis Experiment on Isomerized Heptadecene

Inside an inert atmosphere glovebox, 0.110 g of heptadecene isomers fromExample 46, was mixed with 1 mL of a toluene solution that contained0.001 g of Second Generation Grubbs catalyst. The vial was removed fromthe glovebox, and stirred on a hot plate at 35° C. for two hours. Atoluene solution of butyl vinyl ether was added to quench the reaction.The GC-FID chromatogram, FIG. 66, shows a variety of compounds, expectedfrom this reaction.

Example 54: An Ethylene Cross-Metathesis Experiment on IsomerizedHeptadecene

Inside an inert atmosphere glovebox, 0.108 g of heptadecene isomers fromExample 46, was mixed with 10 mL of a toluene solution and transferredinto a pressure reactor bottle. The bottle was removed from the drybox,purged with ethene and then pressurized to 88 PSI with ethene. Next, 1mL of a toluene solution that contained 0.001 g of First GenerationGrubbs catalyst was injected. The reaction was ran for 2 hours at 35°C., before quenching with a toluene solution of butyl vinyl ether. TheGC-FID chromatogram, FIG. 68, shows a variety of compounds, primarilyα-olefins.

Example 55: A cross metathesis experiment on isomerized methyloctadecenoate

This Example was done using the same method as Example 54. Theisomerized methyl octadecenoate 0.118 g, was made in a similar manner tothat from Example 17. The GC-FID chromatogram, FIG. 70, shows a varietyof compounds, expected from this reaction.

To the extent that the term “includes” or “including” is employed in thedetailed description or the claims, it is intended to be inclusive in amanner similar to the term “comprising” as that term is interpreted whenemployed as a transitional word in a claim. Furthermore, to the extentthat the term “or” is employed in the detailed description or claims(e.g., A or B) it is intended to mean “A or B or both”. When theapplicants intend to indicate “only A or B but not both” then the term“only A or B but not both” will be employed. Thus, use of the term “or”herein is the inclusive, and not the exclusive use. See, Bryan A.Garner, A Dictionary of Modern Legal Usage 624 (2d. Ed. 1995). Forinstance, the isomerization of an alkene with a catalyst or catalystprecursor is determined in a inclusive manner.

While the invention has been described with reference to details of theillustrated embodiment, these details are not intended to limit thescope of the invention as defined in the appended claims.

The embodiment of the invention in which exclusive property or privilegeis claimed is defined as follows:
 1. A process for the production of adecarboxylated unsaturated organic compound, the process comprisingcontacting an unsaturated carboxylic acid in the presence of a catalystor catalyst precursor containing a ruthenium carbonyl carboxylates at atemperature at which decarboxylation occurs and recovering thedecarboxylated unsaturated organic compound product; wherein the numberof C—C double bonds in said decarboxylated unsaturated organic compoundis the same as in said carboxylic acid.
 2. The process of claim 1comprising the additional step of contacting an additional acid to saidcarboxylic acid in the presence of a catalyst or catalyst precursor. 3.The process of claim 2 wherein the acid is a monocarboxylic acid.
 4. Theprocess of claim 3 wherein the monocarboxylic acid is benzoic acid,cinnamic acid, propanoic, acid, undecanoic acid, acetic acid, stearicacid, or oleic acid.
 5. The process of claim 1 wherein thedecarboxylated unsaturated organic compound product is an olefin.
 6. Theprocess of claim 5 wherein the olefin is further subject to anoligomerization or a polymerization reaction.
 7. The process of claim 5wherein the decarboxylated unsaturated organic compound product is amixture of internal and alpha-olefins.
 8. The process of claim 5 whereinthe decarboxylated unsaturated organic compound product is a conjugatedinternal olefin.
 9. A process for the isomerization and decarboxylationof an unsaturated carboxylic acid, the process comprising contacting anunsaturated carboxylic acid in the presence of a catalyst or catalystprecursor containing a ruthenium carbonyl carboxylates at a temperatureat which the isomerization and decarboxylation occurs and recovering theproducts which are isomerized and decarboxylated unsaturated olefins,wherein the C—C double bonds in said isomerized and decarboxylatedunsaturated olefins are in different locations compared to saidunsaturated carboxylic acid, and wherein the number of C—C double bondsin said isomerized and decarboxylated unsaturated olefins are the sameas in said unsaturated carboxylic acid.
 10. The process of claim 9comprising the additional step of contacting an additional acid to saidunsaturated fatty acid in the presence of a catalyst or catalystprecursor.
 11. The process of claim 10 wherein the acid is amonocarboxylic acid.
 12. The process of claim 11 wherein themonocarboxylic acid is benzoic acid, cinnamic acid, propanoic acid,undecanoic acid, acetic acid, stearic acid, or oleic acid.
 13. Theprocess of claim 9 wherein the isomerized and decarboxylated unsaturatedorganic compound product is an olefin.
 14. The process of claim 13wherein the isomerized and decarboxylated unsaturated organic compoundproduct is a mixture of internal and alpha-olefins.
 15. The process ofclaim 13 wherein the isomerized and decarboxylated unsaturated organiccompound product is a conjugated internal olefin.
 16. A process for theproduction of an isomerized unsaturated vegetable oil, the processcomprising contacting a starting unsaturated vegetable oil in thepresence of a catalyst or catalyst precursor containing a rutheniumcarbonyl carboxylates at a temperature at which isomerization occurs andrecovering the isomerized unsaturated vegetable oil product, wherein theC—C double bonds in said isomerized unsaturated vegetable oil are indifferent locations compared to said starting unsaturated vegetable oil,wherein the branching of said isomerized unsaturated vegetable oil isnot increased compared to said starting unsaturated vegetable oil, andwherein the number of C—C double bonds in said isomerized unsaturatedvegetable oil is the same as in said starting unsaturated vegetable oil;wherein said catalyst or catalyst precursor does not contain a phosphineligand.
 17. The process of claim 16 comprising the additional step ofcontacting an additional acid to said vegetable oil in the presence of acatalyst or catalyst precursor.
 18. The process of claim 17 wherein theacid is a monocarboxylic acid.
 19. The process of claim 18 wherein themonocarboxylic acid is benzoic acid, cinnamic acid, propanoic acid,undecanoic acid, acetic acid, stearic acid, or oleic acid.
 20. Theprocess of claim 16 wherein the isomerized vegetable oil is an olefincontaining triglyceride.
 21. The process of claim 20 wherein theisomerized vegetable oil product is a mixture of internal andalpha-olefin containing triglycerides.
 22. The process of claim 20wherein the isomerized vegetable oil product contains a conjugatedinternal olefin.
 23. The process of claim 20, wherein said vegetable oilis soybean oil.
 24. The process of claim 16 wherein the olefin isfurther subject to an oligomerization or a polymerization reaction.